Smoking mixture

ABSTRACT

Tobacco substitute based smoking mixture containing a minimum amount of organic combustible material and a maximum amount of harmless inorganic filler, the composition of the filler having been selected so as to impart a commercially acceptable burning rate to the mixture.

United States Patent [1 1 Borthwick et al.

-451 May 27, 1975 1 SMOKING MIXTURE [73] Assignee: Imperial ChemicalIndustries Limited, London, England [22] Filed: Mar. 18, 1971 [21]App1.No.: 125,872

[30] Foreign Application Priority Data Mar. 23, 1970 United Kingdom13860/70 [52] 11.8. CI 131/2; 131/17;131/14 0C [51] Int. Cl A24b 15/00[58] Field of Search 131/2,15,l7,l40144 [56] References Cited UNITEDSTATES PATENTS 2,809,904 10/1957 Koree 131/2 2,914,072 11/1959 Tyrer etal..... 131/17 2,930,720 3/1960 Finberg 131/17 3,003,895 10/1961Grunwald 131/17 3,106,210 10/1963 Reynolds et a1. 131/17 R 3,112,75412/1963 Diaz 131/2 3,459,195 8/1969 Silberman 1111/]? 3,461,879 8/1969Kirkland 131/2 3,529,602 9/1970 Hind et a1. 131/2 3,545,448 12/1970Mormon 131/22 3,608,560 9/1971 Briskin et al 131/2 OTHER PUBLICATIONSMiano et al., Tobacco Substitute," German Pat. Spec. No. 1,900,491 ofNov. 27, 1969 Abstract.

Primary Examiner-Melvin D. Rein Attorney, Agent, or F irmCushman, Darby& Cushman [5 7] ABSTRACT Tobacco substitute based smoking mixturecontaining a minimum amount of organic combustible material and amaximum amount of harmless inorganic filler, the composition of thefiller having been selected so as to impart a commercially acceptableburning rate to the mixture.

9 Claims, No IDrawings SMOKING MIXTURE This invention relates to smokingmixtures and to methods of producing such mixtures.

Smoking mixtures are systems by which desirable flavours and drugs areconveniently distilled or aerosoled to the mouth during the smokingaction. Being of natural origin, tobacco contains many chemical specieswhich, although necessary for the growth and survival of the plant,contribute nothing to the smoking enjoyment and may unfortunately be theprecursors of chemicals which are injurious to health.

There have been many attempts to lessen the health hazard from tobaccosmoking by adding to the to bacco, chemicals which are reputed tofavourably change the chemical composition and biological activity ofthe smoke.

More recently, substitutes for tobacco have been claimed. See BritishPat. Nos. 1,055,473 and 1,143,500 and U.S. Pat. No. 3,106,209 in whichcellulose, oxidised cellulose and lettuce leaves are used. In thesecompositions, pretreatment and additives are claimed to affect the smokeso that it is acceptable tastewise and is less hazardous to health.

The ideal smoking substitute would be a material or fuel which burnsharmlessly to give the energy to distil, aerosol or pyrolyticallyproduce and distill only the necessary amounts of those componentsrequired for taste and drug effects.

Unfortunately, fuels which burn to give only harmless products aredifficult to find. The most obvious fuel would be elemental carbon whichshould combust to harmless carbon dioxide. Unfortunately again, thecommercially available forms of carbon, e.g. carbon black, are prolificproducers when smoked of polyaromatic hydrocarbons. A large part ofthese hydrocarbons may, of course, come from the impurities produced inthe manufacture of these carbons.

An object of the present invention is to provide a smoking compositionwhich is suitable for aerosoling flavours and drugs but which contains aminimum amount of combustible organic material or smokeproducing fuelwhich on burning inevitably gives rise to some harmful products.

According to the present invention there is provided a smoking mixturecomprising an organic combustible material or fuel, a (on pyrolysis)harmless inorganicfiller and a binder, the inorganic filler beingpresent in quantities such as to considerably reduce the amount ofharmful products produced on combustion of the mixture and thecomposition of the filler having been selected by ion balancing toimpart a commercially acceptable burning rate to the smoking mixture.

The organic combustible material or fuel may comprise to 80 percent byweight of the smoking mixture, preferably -30 percent by weight.

The harmless inorganic filler may comprise 15 to 65 percent by weight ofthe smoking mixture, preferably 40-60 percent by weight.

The mixture may also contain a plasticiser/humectant in addition to thebinder. l

From another aspect, the present invention is a method of manufacturingsaid smoking mixture comprising preselecting a specific organiccombustible material as smoke-producing fuel and preselecting theproportion by weight of said combustible material to be incorporated inthe smoking mixture, admixing said combustible material with apredetermined amount of harmless inorganic filler, the ionic content ofwhich has been balanced to impart a commercially acceptable burning rateto said preselected amount of organic combustible material and finallyforming a shaped arti cle of the mixture utilising a binder.

The shaped article is preferably a film, extruded filament or tape.

For the purpose of this invention the term harmless inorganic filler isintended to include inorganic salts of some relatively simple organicacids. For example, formates, oxalates, tartrates and citrates can beused as harmless inorganic fillers but these are less satisfactory thanthe preferred completely inorganic materials on account of someundesirable pyrolytic decomposition. This decomposition becomespotentially more harmful as the size of the organic molecule increases.

The inorganic filler preferably comprises a mixture of two or more suchinorganic salts admixed in quantities such as to obtain the balance ofanions and cations most appropriate for imparting the desirable rate ofcombustion to the preselected amount of the specific organic combustiblematerial incorporated in the smoking mixture.

By way of example, an acceptable rate of combustion for the smokingmixture of the invention can be correlated to the puff number of 10-12of a machine-made standard Class B British cigarette containing 1.1 g.tobacco, where each puff is of 25 ml. volume in two seconds, followed bya 58 second rest or smouldering period and where the mm. cigarette issmoked to a butt length of 20 mm.

The smoking mixture of the invention is intended to be used as acomparatively safe neutral substrate which burns at a correct rate andhas a low content of relatively harmless organic fuel and a high contentof harmless inorganic filler. Flavourants, drugs, medicaments, materialsto improve ash coherence and colour and other additives, includingtobacco, can be incorporated as desired to produce the final productsold to the smoker.

The smoking mixture containing such a high content of harmless inorganicmaterial can advantageously be produced by a process similar toreconstituted tobacco processes which utilise film-forming agents orbinders. Such a film-forming process enables a relatively largeproportion of inorganic materials to be incorporated into the smokingmixture.

The film-forming agent or binder and the plasticiserlhumectantincorporated in the mixture are also organic in nature but they may havean inorganic content and they can be carefully chosen from materialsknown to burn to produce lesser amounts of harmful products thantobacco.

Preferred binders include carboxymethyl cellulose and its salts andother carboxylated carbohydrates. Where the amount of binder employed isvery small other less satisfactory binder materials such as naturalgums, guar gums, locust bean gums and other synthetic binders such asmethyl and other ethers of cellulose may be used.

Preferred plasticiser/humectants include glycerol, ethylene glycol andpolyethylene glycol.

Organic combustible materials suitable as smokeproducing fuel in themixtures of the invention include carbohydrates, modified carbohydratesand certain aldol condensation products. Carbon samples which producelower amounts of polycyclic aromatic hydrocarbons can also be used.

The smoke-producing carbohydrate may advantageously comprise cellulose,cellulose derivatives, sugars, starch, alginate, pectin, natural gum,glucuronic acid or polygalacturonic acid.

The modified carbohydrate may advantageously be prepared as disclosed inour US. Pat. No. 1,1 13,979 by subjecting it to a catalysed degradationprocess at a temperature of lO-250C until the weight of the degradedmaterial is less than 90 percent of the dry weight of the originalcarbohydrate.

Preferred degradation catalysts include sulphuric acid, sulphamic acidand ammonium sulphamate. The modified carbohydrate may be oxidisedcellulose.

The aldol condensation products may advantageously be prepared by acidor based catalysed condensation of a compound of the formula RCOCH CH-COR (I) (or a precursor thereof) wherein R and R which may be the sameor different, each represent a hydrogen atom, or an alkyl, hydroxyalkylor formyl group.

Preferably, the aldol condensation product comprises the condensate fromsuccinaldehyde, acetonyl acetone or the condensate from a precursor of(1) which is a compound containing a furan ring structure.

A further object of the present invention is to utilise the combustionmodifying properties of known inorganic fillers to reduce the quantityof health hazard chemicals in smoking compositions, this object beingattained by reducing the amount of organic fuel in the smoking mixturesand making up the weight with said inert fillers.

The choice of the inert inorganic fillers to be incorporated in thesmoking mixture determines the rate of combustion or how many normalpuffs can be had from a given weight of the mixture.

The art of making an acceptable burning composition involves choosingthe correct proportions of fillers which relatively promote or retardthe combustion.

Earlier publications in the tobacco substitute field have suggested thatburning control of tobacco substitutes is exerted through hydrated metalsalts. The use of such materials as alkali nitrates to improve thefireholding of tobacco blends is well known. It has also been suggestedthat potassium is an essential constituent for the proper burning oftobacco. It is our experience that the water content of tobaccosubstitutes has only a relatively small effect on the number of puffsgiven by a particular weight of cigarette but may determine whether acomposition is glowproofed or burns satisfactorily. Hydrated andnon-hydrated versions of the same salt can be used. On the other hand,we have found that burning control is strongly influenced by the natureof the combination of cations and anions present. This does not implythat the combustion rate is uninfluenced by other considerations such asfuel particle size or texture of the smoking material.

The art of retarding combustion without making a composition glowproofyet obtaining the correct puff count from a given weight of smokingmixture by the use of these inert fillers is another key to the successof the present invention. Combustion accelerators are combined withcombustion retardants in proportions which give a desirable rate ofcombustion for a specific organic fuel and a particular amount thereofin the mixtures. Whilst this principle of the invention is described andillustrated herein with reference to commonly available inert fillers,this principle can be applied to any inorganic material which proves tobe a safe filler for use in a smoking mixture.

It is impossible to specify that some ionic species retard while othersaccelerate glow combustion since some fuels do not sustain combustion inisolation. It suffices to say that we have found that with a number offuels a number of commonly available acidic anions influence combustionrate and that the order of the retarding ability of a selection of themis formate oxalate s silicate carbonate chloride sulphate phosphateborate. Isolated exceptions to these orders indicated can, however, befound. Amongst the cations the order is sodium=potassium calciummagnesium. With the cations it would appear their effect on the burningrate depends on their basicity, the most significant change being fromcalcium to magnesium.

This implies, for example, that in smoking mixtures which are identicalexcept that A contains sodium sulphate and B contains the sameproportion by weight of magnesium sulphate, A will burn away morequickly. Similarly, in two compositions identical except that A containscalcium carbonate and B contains calcium borate, Composition A will burnaway more quickly than Composition B.

The fillers chosen should not have the power to retain excessivequantities of water, otherwise glowproofing will result.

It is preferable, but not essential, that the fillers should beinsoluble in water. Calcium carbonate has been found to be a most usefulagent for use as a combustion accelerator balanced against combustionretarding agents such as calcium orthophosphate (CaH- P0 211 0),magnesite (MgCO light basic magnesium carbonate (3MgCO .Mg.(Ol-1) .3HO), and calcium sulphate (CaSO /2H O). Using these and other inorganicmaterials, films can be made which give shred with filling powerscomparable to tobacco shred.

Although the above description and the Examples which follow illustratethe required balance of ions being obtained by varying the respectiveamounts of two inorganic salts, it is possible that a suitable rate ofcombustion for a smoking mixture could be attained using an optimumamount of a single inorganic salt as inert filler.

The main advantages of the smoking mixtures of the invention comparedwith earlier synthetic products and, of course, tobacco, are as follows:

a. The lower amounts of organic materials present mean thatproportionately lower amounts of the harmful smoke products are formedwhilst maintaining a desirable rate of combustion for the mixture. Inthis connection, tests carried out on smoking mixtures of the inventionshow a reduction in the benzpyrene content of the smoke and a reductionin other chemical species known or suspected to be harmful because ofthe reduced organic fuel content. Furthermore, the mixtures of theinvention advantageously have the same burning characteristics astobacco based smoking mixtures. They keep lit and continue to burn andthey have the same rate of combustion as tobacco.

b. The lower amounts of organic materials present gave rise to loweramounts of any odour off notes" which may arise from smoking thesematerials (e.g. the burnt paper note of cellulose). Lower amounts ofadded masking agents are required in these instances.

c. The process of the invention permits the use of fuels which werepreviously impossible to use on account of their physical properties, e.g. the high solubility and non-fibrous nature of sucrose, glucose andglucuronic acid. The high inorganic content gives body to the films ofthese materials which were previously unusable in smoking mixtures.

The principle of ion balancing of the inert fillers is illustrated inthe following tables. According to this principle the specific fuel andthe amount thereof to be used in the mixture are first selected and thenion balance tests are effected to determine the composition having themost desirable rate of combustion. As can be seen from the tables theions are investigated separately to ascertain their relativesuitabilities for the selected fuel.

Tables 1 to 5 illustrate the comparative retarding powers of cations ofvarious inert fillers when added to a smoking mixture of the followingcomposition:

by weight Thermally degraded cellulose* 53 SCMC Glycerol 14 Calciumcarbonate 5 Citric acid 4 Potassium citrate 5 Ammonium sulphate 4 Thethermally degraded cellulose was prepared as follows and in accordancewith the method described in our British Patent Specification No.1,113,979. 1,0 part by weight of sheeted alpha-cellulose was immersed ina 50% aqueous Solution of ammonium sulphamate and the pulp compressedbetween rolls to leave 1.0 part of solution in the pulp. The pulp wasairdried at 45C and then heated at 240C so that the pulp became blackand the weight of the degraded material was 75% of the original weightof alpha-cellulose plus ammonium sulphamate. The black pulp sheet wasallowed to cool and was then ground to a powder passing a 120 BSS sieve.

In each case the inorganic filler constituted 5 percent of the totalweight of the smoking mixture. The effect of the basicity of the cationis clearly indicated in each table.

Table l added Filler (by weight) Basicity of cation Puff number MgSO 7HO 5 increasing 23 CaSO.,.%H,O 5 14.5 K 80 5 14.3 Na SO 5 14.25

Table 2 added Puff Filler (by weight) Basicity of cation number Mg (PO 5increasing 18.2 CaHPO,.2H O 5 16.0 Na HlO 5 I 16.0 Na HPO .l2H O 5 15.0

Table 3 added Basicity Filler (by weight) of cation Puff number CaB O, 5increasing 19.8 Na mo, 5 I: 19.8 Na B O 101-1 0 5 17.0

Tables 6 to 8 illustrate the retardant properties of different anions.The same basic smoking mixture of Tables l to 5 was used in the testsfor Tables 6 to 8.

Table 6 Effectiveness of Puff Filler added anion number CaP O 5decreasing retardant properties 19.8 CaHPO,.2H O 5 ditto 16.0 CaSO .%H O5 ditto 14.5 CaCO:, 5 ditto 12.0 CaCl .6H O 5 ditto 1 1.5 Ca Oxalate 5ditto l 1.0 Ca Formate 5 ditto 9 Table 7 Effectiveness of Puff Filleradded anion number Na B O 5 decreasing retardant properties 19.8 Nal-[P0 5 ditto l 6.0 Na SO 5 ditto 14.25 NaCl 5 ditto 10.8 Na CO 5 ditto1 0.4 Na SiO 5 ditto 9.4

Table 8 Effectiveness of Puff Filler added anion number Mg (PO 5decreasing retardant properties 18.2 MgSO .7H O 5 ditto 1 7.5 MgCO; 5ditto l 5.0 MgCl .6l-l O 5 ditto 1 3.0 Mg Silicate 5 ditto 12.0 MgOxalate 5 ditto 12.0 Mg Formate 5 ditto 10.8

A second smoking mixture was prepared of similar composition to thatutilised for the tests of Tables 1 to 8 but with 53 parts by weightthermally degraded cellulose replaced by 53 parts by weight carbon blackas fuel. Tests similar to those of Tables 1 to 8 were carried out on thecarbon black based smoking mixture and the results are indicated in thefollowing Tables 1a, 2a, 4a, 6a and 8a which correspond respectively toTables 1, 2, 4, 6 and 8. No Tables corresponding to Tables 3, 5 and 7were produced.

Table la Table 8a Filler added Basicity of cation Puff numberEffccthflcness 9f Puff Filler added anion number MgSO .7H O 5 increasing1 1.7 S CaSO4 i/2H2O 5 Mg;,(PO decreasing retardant properties 16.7 SO 5g5 MgSO .7H O 5 ditto llr7 K2304 5 g3 MgCl .6H O 5 ditto 10.3 MgCO 5ditto 9.2 Mg Silicate 5 ditto 9.0 Mg Oxalate 5 ditto 8.6 Mg Formate 5ditto 7.8

The following Tables 9 and 9a illustrate the effect of the ratio ofpercent CaCO percent Cal-lPO .2H O on Table 2a the uff number resectivel of thermal] de raded P Y 8 cellulose based smoking mixtures andcarbon black Flue added l of Puff number based smoking mixtures. In thecase of Table 9 it is to Mgqwom 5 increasing 167 be noted that 15-17 isthe correct puff number for Cal-lPO .2H O 5 14.7 hand rolled cigarettesmade wlth commercially avail- NazHPO 5 H able hand rolling paper incontrast to machine made Na HPO .l2H O 5 9.5 0

cigarettes which have a puff number of 12.

Table 9 thermally degraded cellulose 28 28 28 28 28 28 SCMC l0 l0 l0 l0l0 l0 Glycerol l4 l4 l4 l4 l4 l4 %CaCO l0 l2 l4 l6 18 2O CaHPO .2H O 2321 l9 l7 l5 K citrate 4 4 4 4 4 4 Citric acid 4 4 4 4 4 4 (NH4)2SO4 5 55 5 5 5 Ratio CaCO:

CaHPO .2H O 1:2.5 l:l.92 lzlr5 l:l.l9 1:0.94 120.75 Puffnumber l7l8l6-l7 l516 14-15 l3l4 Glow- Correct puff too low proofed numbers puffnumber The smoking mixtures above were hand rolled with papercommercially available in Britain for this purpose. For comparisonpurposes 1.1 g. hand rolled tobacco cigarettes give l5- l7 puffs. 1.1 g.machine made cigarettes with the more porous paper used by UnitedKingdom cigarette manufacturers give 10-12 puffs.

Table 9a Carbon black 28 28 28 28 28 28 SCMC 10 10 10 10 10 10 Glyceroll4 l4 l4 l4 l4 l4 %CaCO l0 l2 14 16 18 2O %CaHPO .2H O 25 23 2| 19 l7 l5K Citrate 4 4 4 4 4 4 Citric acid 4 4 4 4 4 4 (NHJZSQ, 5 5 5 5 5 5 RatioCaCO CaHPO .2H O 112.5 11192 1:15 11.19 1:0.94 1:0.75 Puff number ll-l210-1] 10 9-10 8-9 7-8 Correct puff No. range too low puff No.

Table 4a The five compositions indicated in Table 9 and Table I 9a ashaving a correct puff number constituted the first Filler added Basicityof cation P ff number five Examples of smoking mixtures of theinvention. M CO 5 Tables 9 and 9a thus serve to illustrate how the ionbal- 5 if 2:? ancing principle of the present invention is applied.

Applying the principle illustrated in Tables 9 and 9a Table 6a andutilising the information given in the earlier tables a further sevenexamples of smoking mixtures accord- Effectiveness of Puff ing to theinvention were prepared, the compositions Filler added anion nu her andpreparations of which are illustrated in Examples I 6 to 23 below. gzggzi g decreasmg 5 52 propcrlles lg; In Examples 6 to 9 the organic fuelis thermally de- 4' 2 Ca Oxalate 5 92 graded cellulose preparedaccording to the method Ca Formate 5 ditto 7.0 reviousl described withre ard to Tables 1 to 9. In CaCO; 5 ditto 6,7 p y g Examples 10 to 13the organic fuels are respectively sucrose, glucose, alpha-cellulose andpolygalacturonic acid.

In each of Examples 6 to 13 the final composition as aforesaid wasreached after tests similar to those indicated in Tables 9 and 9a hadbeen effected. The compositions actually illustrated in Examples 6 to 13are those having the best puff numbers. Examples 14 to 23 illustratefurther variations in the parameters of the in vention.

EXAMPLE 6 5.38 parts thermally degraded cellulose powder, 4.26 partspowdered chalk, 7.10 parts powdered magnesium carbonate and 60 partswater were stirred together. 1.34 parts glycerol and 20 parts water werestirred together then added to the previous mixture. The whole waspaddle-stirred together for 30 minutes.

The mixture was transferred to a Probst & Class mill and at a gapsetting of 2, milled for minutes. The gap was reduced to setting Zeroand the mixture milled for a further 5 minutes. At the end of thisperiod, 1.92 parts SCMC were added quickly into the centre of the vortexand the slurry immediately discharged into a clean container then paddlestirred for 15 minutes. Sufficient water was then added to reduce theviscosity to 55,000 cps.

Film material was made by spreading the slurry at 0.020 in. on aband-drier and drying by means of hot air at 150C. The band speed was 19ft. min. The film material was shredded and processed satisfactorily oncigarette making machinery.

1.1 g. cigarettes gave standard puffs. The smoke was mild to taste.

Dry weight composition of Example 6:

Thermally degraded cellulose 26.9 SCMC 9.6 Glycerol 6.7 CaCO; 21.3 MgCO35.5

EXAMPLE 7 5.38 parts thermally degraded cellulose powder, 3.84 partspowdered chalk, 6.72 parts powdered light basic magnesium carbonate and60 parts water were stirred together. 1.36 parts glycerol, 0.78 partpotassium citrate and 20.0 parts water were stirred together, then addedto the previous mixture. The whole was paddlestirred together for 30minutes.

The mixture was transferred to a Probst & Class mill and at a gapsetting of 2, stirred for 5 minutes. The gap was reduced to zero and themixture milled for a further 5 minutes. At the end of this time, 1.92parts SCMC were added quickly into the vortex and the slurry immediatelydischarged into a clean container. The slurry was paddle-stirred forminutes. Sufficient water was then added to reduce the viscosity to50,000

Film material was made by spreading the slurry at 0.020 in. on aband-drier and dried by hot air at 150C. The band speed was 19 ft. min..

The film material was shredded and processed satisfactorily on cigarettemaking machinery.

1.1 g. cigarettes gave 10 standard puffs. The smoke was mild to taste.

Dry weight composition of Example 7:

7r Thermally degraded cellulose 26.9 SCMC 9.6 Glycerol 6.7 CaCO 19.33.MgCO .Mg(OH) .3H O 33.6 K Citrate 3.9

EXAMPLE 8 4.08 parts thermally degraded cellulose powder, 4.34 partspowdered chalk, 5.75 parts calcium hydrogen orthophosphate and 60 partswater were stirred together. 2.33 parts glycerol, 0.57 part potassiumcitrate, 0.72 part citric acid, 0.57 part ammonium sulphate and 20 partswater were stirred together then added to the previous mixture. Thewhole was stirred together for 30 minutes.

The mixture was transferred to a Probst & Class mill and at a gapsetting of 2 milled for 5 minutes. The gap was reduced to zero and themixture milled for a further 5 minutes. At the end of this period 1.76parts SCMC were quickly added into the centre of the vortex and theslurry immediately discharged into a clean container, thenpaddle-stirred for 15 minutes. The viscosity was 42.000 ops.

Film material was made by spreading the slurry at 0.010 in. on aband-drier and drying by means of hot air at C. The band speed was 22ft. min..

The film material was shredded and processed satisfactorily on cigarettemaking machinery.

1.1 g. cigarettes gave 10 standard puffs. The smoke was mild to taste.

Dry weight composition of Example 8:

Thermally degraded cellulose 50 parts thermally degraded cellulosepowder, 3.2 parts powdered chalk, 5.7 parts powdered magnesiumcarbonate, 0.95 part powdered bentonite and 70.0 parts water werestirred together. 1.25 parts glycerol, 0.7 part potassium citrate and11.5 parts water were stirred together and then added to the previousmixture. The whole was stirred together for 15 minutes.

The mixture was transferred to a Probst & Class mill and at a gapsetting of 2 milled for 5 minutes. The gap was now reduced to zero andthe mixture milled for a further 5 minutes. At the end of this time, 1.7parts SCMC were added quickly into the centre of the vortex and theslurry immediately discharged into a clean container. The slurry waspaddle-stirred for 15 minutes and at the end of this period sufficientwater was added to reduce the viscosity to 60,000 cps.

Film material was made by spreading the slurry at 0.020 in. on aband-drier and drying by means of hot air at 150C. The band speed was 16ft. min".

The film material was shredded and processed satisfactorily on cigarettemaking machinery.

1.1 g. cigarettes gave 1 1 standard puffs. The smoke was mild to taste.

The dry weight composition of Example 9 was:

Thermally degraded cellulose 26.9 SCMC 9.6 Glycerol 6.7 CaCO 17.3 MgCO30.6 Bentonite 5.0 K Citrate 3.9

EXAMPLE 10 5.6 parts sucrose, 7.8 parts calcium carbonate, 2.0 partslight basic magnesium carbonate, 0.8 part potassium citrate, 1.1 partscitric acid and 0.8 part ammonium sulphate were stirred for half an hourwith 68.6 parts of water. The mixture was transferred to a probst &Class mill and at a gap setting of 2 milled for 5 minutes. The gap wasreduced to setting zero and the mixture milled for a further 5 minutes.At the end of this time 2.0 parts SCMC were added quickly and the slurrydischarged immediately into a container and paddlestirred for 15minutes. 11.3 parts of water were added to reduce the viscosity to56,000 cps.

Film material was prepared by spreading the slurry at 0.018 in. on aband-drier and drying by means of air at 60C. The band speed was 9ft./min.

The film material was very sensitive to moisture. It could, however, besatisfactorily shredded and processed by cigarette making machinery ifthe relative humidity of the atmosphere was maintained at 58-60 RH and60F. Under these conditions the equilibrium moisture content of theshred was 6.3-6.8.

1.1 g. cigarettes gave 10 puffs. The smoke from the cigarettes was mildto taste.

The dry weight composition of Example 10 was:

Sucrose 28 SCMC 10 CaCO 39 Light basic Mg carbonate 10 K citrate 4Citric acid 5 (NI-10 50., 4

EXAMPLE 1 l 5.5 parts glucose, 7.6 parts calcium carbonate, 2.0 partslight basic magnesium carbonate, 0.75 part potassium citrate, 0.75 partammonium sulphate and 1.0 part citric acid were stirred for half an hourwith 67.2 parts of water. The mixture was transferred to a Probst &Class mill and at a gap setting of 2 milled for 5 minutes. The gap wasreduced to setting zero and the mixture milled for a further 5 minutes.At the end of this time 20 parts SCMC were added quickly and the slurrydischarged immediately into a container and paddlestirred for minutes.13.3 parts of water were added to reduce the viscosity to 60,000 cps.

Film material was prepared by spreading the slurry at 0.020 in. on aband drier and drying by means of air at 150C. The band speed was 18ft./min.

The film material was very sensitive to moisture. It could, however, besatisfactorily shredded and processed by cigarette making machinery ifthe relative humidity of the atmosphere was maintained at 53-55 percentRH and 60F. Under these conditions the equilibrium moisture content ofthe shred was 5-6.

1.1 g. cigarettes gave 10 puffs. The smoke from the cigarettes was mildto taste.

Dry weight composition of Example 11:

Glucose 28 SCMC 10 CaCO 39 Light basic Mg carbonate 10 K citrate 4Citrate acid 5 02 4 4 EXAMPLE 12 4.5 parts alpha-cellulose powder, 3.5parts chalk, 5.1 parts calcium hydrogen orthophosphate, 2.5 partsglycerol, 0.8 part citric acid, 0.7 part ammonium sulphate, 0.7 partpotassium citrate and 71 parts water were stirred together for half anhour. The mixture was transferred to a Probst & Class mill and at a gapsetting of 2 milled for 5 minutes. The gap was reduced to setting zeroand the mixture milled for a further 5 minutes. At the end of thisperiod 1.7 parts of SCMC were added quickly and the slurry dischargedimmediately into a container and paddle-stirred for 15 minutes. 9.5parts of water were added to reduce the viscosity to 46,000 cps.

Film material was made by spreading the slurry at 0.012 in. on aband-drier and drying by means of hot air at C. The band speed was 20ft./min.

The film material was shredded and processed satisfactorily on cigarettemaking machinery.

1.1 g. cigarettes gave 10 standard puffs. The smoke from the cigaretteswas mild.

The dry weight composition of Example 12 was:

Alpha-cellulose SCMC Glycerol CaCO CaHPO,,.2H O K citrate Citric acid(NH4)2SO4 EXAMPLE 13 2.04 parts of glycerol and 1.17 parts potassiumcitrate were dissolved in 250 mls. of water. 2.88 parts of SCMC werethen added to the solution and stirred for 15 minutes. 8.07 parts ofalginic acid, 10.08 parts of magnesium carbonate and 5.76 parts powderedchalk were mixed together in the dry state, then added to the previousmixture. The whole was stirred for 1 hour.

Film material was made by spreading the slurry at 0.02 inches on glassplates and left to dry. The film material was humidified and shredded.Ten cigarettes were hand rolled with Imperial Verge paper.

1.1 g. cigarettes gave 11 standard puffs. The smoke was mild to taste.

Dry weight composition:

Alginic acid 26.9 Glycerol 6.8 SCMC 9.6

-Continued CaCO 19.2 M co 33.6 Potassium Citrate 3.9

EXAMPLE 14 2.04 parts of glycerol and 1.17 parts of potassium citratewere dissolved in 150 mls. of water. 2.88 parts of SCMC were then addedto the solution and stirred for 15 minutes. 8.07 parts of thermallydegraded sucrose, 10.08 parts of magnesium carbonate and 5.76 parts ofpowdered chalk were mixed together in the dry state then added to theprevious mixture. The whole was stirred for 1 hour.

Film material was made by spreading the slurry at 0.02 inches on glassplates and left to dry. The film material was humidified and shredded.Ten cigarettes were hand rolled with Imperial Verge paper.

1.1 g. cigarettes gave standard puffs.

Dry weight composition:

Thermally degraded sucrose 26.9 Glycerol 6.8 SCMC 9.6 CaCO 19.2Potassium Citrate 3.9 Magnesite 33.6

EXAMPLE 2.04 parts of glycerol and 1.17 parts of potassium citrate weredissolved in 150 mls. of water. 2.88 parts of sodium alginate were thenadded to the solution and stirred for 15 minutes. 8.07 parts ofthermally degraded cellulose, 11.88 parts of magnesium carbonate and3.96 parts powdered chalk were mixed together in the dry state thenadded to the previous mixture. The whole was stirred for 1 hour.

Film material was made by spreading the slurry at 0.02 inches on glassplates and left to dry. The film material was humidified and shredded.Ten cigarettes were hand rolled with Imperial Verge paper.

1.1 g. cigarettes gave 10 standard puffs. The smoke was mild to taste.

Dry weight composition:

' Thermally degraded cellulose 26.9 Glycerol 6.8 Sodium Alginate 9.6CaCO 13.2 Potassium citrate 3.9 MgCO 39.6

EXAMPLE 16 2.04 parts of glycerol and 1.17 parts of potassium citratewere dissolved in 75 mls. of water. 2.88 parts 10- cust bean gum werethen added to the solution and stirred for 15 minutes. 8.07 parts ofthermally degraded cellulose, 12.66 parts magnesium carbonate and 3.18parts powdered chalk were mixed together in the dry state then added tothe previous-mixture. The whole was stirred for 1 hour.

Film material was made by spreading the slurry at 0.02 inches on glassplate and left to dry. The film material was humidified and shredded.Ten cigarettes were hand rolled with Imperial Verge paper.

14 1.1 g. cigarettes gave 10 standard puffs. The smoke was mild totaste. Dry weight composition:

Thermally degraded cellulose 26.9 Glycerol 6.8 Locust Bean Gum 9.6 CaCO10.6 Potassium Citrate 3.9 MgCO 42.2

EXAMPLE 17 2.04 parts glycerol and 1.17 parts potassium citrate weredissolved in mls. of water. 2.88 parts methyl cellulose were then addedto the solution and stirred for 15 minutes. 8.07 parts thermallydegraded cellulose; 12.66 parts magnesium carbonate and 3.18 partspowdered chalk were mixed together in the dry state, then added to theprevious mixture. The whole was stirred for 1 hour.

Film material was made by spreading the slurry at 0.02 inches on glassplates and left to dry. The film material was humidified and shredded.Ten cigarettes were hand rolled with Imperial Verge paper.

1.1 g. cigarettes gave 11 standard puffs. The smoke was mild to taste.

Dry weight composition:

- v Thermally degraded cellulose 26.9 Glycerol 6.8 Methyl Cellulose 9.6CaCO 10.6 Potassium Citrate 3.9 MgCO 42.2

EXAMPLE 18 2.04 parts glycerol and 1.17 parts potassium citrate weredissolved in 150 mls. of water. 2.88 parts SCMC were then added to thesolution and stirred for 15 minutes. 8.07 parts thermally degradedcellulose, 5.76 parts ferrous sulphate and 10.08 parts magnesiumcarbonate were mixed together in the dry state, then added to theprevious mixture. The whole was stirred for 1 hour.

Film material was made by spreading the slurry at 0.02 inches on glassplatesand. left to dry. The film material was humidified and shredded.Ten cigarettes were hand rolled with Imperial Verge paper.

1.1 g. cigarettes gave 11 standard puffs. The smoke was mild to tasteDry weight composition:

Thermally degraded cellulose 26.9 Glycerol 6.8 Potassium citrate 3.9SCMC 9.6 FeSO, 19.2 MgCO; 33.6

EXAMPLE 19 2.04 parts glycerol and 1.17 parts potassium citrate weredissolved in 150 mls. of water. 2.88 parts SCMC were then added to thesolution and stirred for 15 minutes. 8.07 parts thermally degradedcellulose, 10.08 parts aluminium hydroxide and 5.76 parts powdered chalkwere mixed together in the dry state, then added to the previousmixture. The whole was stirred for 1 hour.

Film material was made by spreading the slurry at 0.02 inches on glassplates and left to dry. The film material was humidified and shredded.Ten cigarettes were hand rolled with Imperial Verge paper.

1.1 g. cigarettes gave 12 standard puffs. The smoke was mild to taste.

Dry weight composition:

Thermally degraded cellulose 26.9 Glycerol 6.8 Potassium citrate 3.9SCMC 9.6 CaCO 19.2 AL(OH) 33.6

EXAMPLE 20 2.04 parts glycerol and 1.17 parts potassium citrate weredissolved in 150 mls. of water. 2.88 parts SCMC were then added to thesolution and stirred for 15 minutes. 8.07 parts thermally degradedcellulose, 7.56 parts magnesium carbonate and 8.16 parts titaniumdioxide were mixed together in the dry state, then added to the previousmixture. The whole was stirred for 1 hour.

Film material was made by spreading the slurry at 0.02 inches on glassplates and left to dry. The film material was humidified and shredded.Ten cigarettes were hand rolled with Imperial Verge paper.

1.1 g. cigarettes gave standard puffs. The smoke was mild to taste.

Dry weight composition:

Thermally degraded cellulose 2 Glycerol SCMC Potassium citrate Titaniumdioxide Magnesium carbonate EXAMPLE 21 2.04 parts glycerol and 1.17parts potassium citrate were dissolved in 150 mls. of water. 2.88 partsSCMC were then added to the solution and stirred for minutes. 8.07 partsthermally degraded cellulose, 11.28 parts magnesium carbonate and 4.56parts aluminosilicate were mixed together in the dry state, then addedto the previous mixture. The whole was stirred for 1 hour.

Film material was made by spreading the slurry at 0.02 inches on glassplates and left to dry. The film material was humidified and shredded.Ten cigarettes were hand rolled with Imperial Verge paper.

1.1 g. cigarettes gave 12 standard puffs. The smoke was mild to taste.

Dry weight composition:

Thermally degraded cellulose 2 Glycerol SCMC Potassium citrateAluminosilicate Magnesium carbonate What we claim is:

l. A smoking mixture in fabricated form comprising a. as smoke-producingfuel, a particulate solid thermally degraded carbohydrate tobaccosubstitute which is obtained by subjecting a carbohydrate to a catalyseddegradation process at a temperature of at least 100C until the weightof the degraded material is less than 90 percent of the dry weight ofthe original carbohydrate,

b. a harmless filler and 0. sufficient binder to enable the mixture tobe fabricated,

said filler being harmless on pyrolysis and present in a proportion of40 to 65 percent by weight of the mixture and being selected from saltswherein the anion comprises formate, oxalate, citrate, tartrate,silicate, carbonate, chloride, sulphate, phosphate, borate, oxide,dioxide or aluminate and the cation comprises sodium, potassium,calcium, magnesium, iron or titanium, the combination of cations andanions in the filler being selected to impart a burning rate correlatedto a puff number of 8-12 of a machine-made standard Class B Britishcigarette containing 1.1 g. tobacco, where each puff is of 25 ml. volumein two seconds, followed by a 58 second rest or smouldering period andwhere the mm. cigarette is smoked to a butt length of 20 2. A smokingmixture as claimed in claim 1 wherein the filler comprises calciumcarbonate, calcium borate, sodium borate, calcium orthophosphate,calcium oxalate, iron sulphate, titanium dioxide, magnesium carbonate,sodium aluminosilicate, bentonite or aluminium hydroxide.

3. Atsrnoking mixture as claimed in claim 1 wherein the harmless fillercomprises a mixture of calcium carbonate and a member of the groupconsisting of magnesite, light basic magnesium carbonate, calciumorthophosphate and calcium sulphate, and the binder is carboxymethylcellulose or salt thereof.

4. A smoking mixture as claimed in claim 1 comprising aplasticiser/humectant in addition to the binder.

5. A smoking mixture as claimed in claim 4 wherein theplasticiser/humectant comprises glycerol, ethylene glycol orpolyethylene glycol.

6. A smoking mixture as claimed in claim 1 wherein the binder comprisescarboxymethyl cellulose and its salts, other carboxylated carbohydrates,natural gum, guar gum, locust bean gum or cellulose ethers.

7. A method of manufacturing a smoking mixture according to claim 1comprising preselecting a particulate solid thermally degradedcarbohydrate tobacco substitute as defined in claim 1 as smoke-producingfuel and preselecting the proportion by weight of said thermallydegraded carbohydrate tobacco substitute to be incorporated in thesmoking mixture, admixing said combustible material with a predeterminedamount of binder and a harmless filler selected from salts wherein theanion comprises formate, oxalate, citrate, tartrate, silicate,carbonate, chloride, sulphate, phosphate, borate, oxide, dioxide oraluminate and the cation comprises sodium, potassium, calcium,magnesium, iron or titanium, the filler being harmless on pyrolysis andpresent in a proportion of 40 to 65 percent by weight of the mixture,and the combination anions and cations in the filler being sufficient toimpart a burning rate correlated to a puff number of 8-l 2 of amachine-made shaped article is a film, extruded filament or tape.

9. A method as claimed in claim 7 wherein the filler comprises calciumcarbonate, calcium borate, sodium borate, calcium orthophosphate,calcium oxalate, iron sulphate, titanium dioxide, magnesium aluminate,so-

dium aluminium silicate or mixture thereof.

1. A SMOKING MIXTURE IN FABRICATED FORM COMPRISING A. AS SMOKE-PRODUCINGFUEL, A PARTICULATE SOLID THERMALLY DEGRADED CARBOHYDRATE TOBACCOSUBSTITUTE WHICH IS OBTAINED BY SUBJECTING A CARBOHYDRATE TO A CATALYSEDDEGRADATION PROCESS AT A TEMPERATURE OF AT LEAST 100*C UNTIL THE WEIGHTOF THE DEGRADED MATERIAL IS LESS THAN 90 PERCENT OF THE DRY WEIGHT OFTHE ORIGINAL CARBOHYDRATE, B. A HARMLESS FILLER AND C. SUFFICIENT BINDERTO ENABLE THE MIXTURE TO BE FABRICATED, SAID FILLER BEING HARMLESS ONPYROLYSIS AND PRESENT IN A PROPORTION OF 40 TO 65 PERCENT BY WEIGHT OFTHE MIXTURE AND BEING SELECTED FROM SALTS WHEREIN THE ANION COMPRISESFORMATE, OXALATE, CITRATE, TARTRATE, SILICATE, CARBONATE, CHLORIDE,SULPHATE, PHOSPHATE, BORATE, OXIDE, DIOXIDE OR ALUMINATE AND THE CATIONCOMPRISES SODIUM, POTASSIUM, CALCIUM, MAGNESIUM, IRON OR TITANIUM, THECOMBINATION OF CATIONS AND ANIONS IN THE FILLER BEING SELECTED TO IMPARTA BURNING RATE CORRELATED TO A PUFF NUMBER OF 8-12 OF A MACHINE-MADESTANDARD CLASS B BRITISH CIGARETTE CONTAINING 1.1 TOBACCO, WHERE EACHPUFF IS OF 25 ML. VOLUME IN TWO SECONDS, FOLLOWED BY A 58 SECOND REST ORSMOULDERING PERIOD AND WHERE THE 70 MM. CIGARETTE IS SMOKED TO A BUTTLENGTH OF 20 MM.
 2. A smoking mixture as claimed in claim 1 wherein thefiller comprises calcium carbonate, calcium borate, sodium borate,calcium orthophosphate, calcium oxalate, iron sulphate, titaniumdioxide, magnesium carbonate, sodium aluminosilicate, bentonite oraluminium hydroxide.
 3. A smoking mixture as claimed in claim 1 whereinthe filler harmless comprises a mixture of calcium carbonate and amember of the group consisting of magnesite, light basic magnesiumcarbonate, calcium orthophosphate and calcium sulphate, and the binderis carboxymethyl cellulose or salt thereof.
 4. A smoking mixture asclaimed in claim 1 comprising a plasticiser/humectant in addition to thebinder.
 5. A smoking mixture as claimed in claim 4 wherein theplasticiser/humectant comprises glycerol, ethylene glycol orpolyethylEne glycol.
 6. A smoking mixture as claimed in claim 1 whereinthe binder comprises carboxymethyl cellulose and its salts, othercarboxylated carbohydrates, natural gum, guar gum, locust bean gum orcellulose ethers.
 7. A method of manufacturing a smoking mixtureaccording to claim 1 comprising preselecting a particulate solidthermally degraded carbohydrate tobacco substitute as defined in claim 1as smoke-producing fuel and preselecting the proportion by weight ofsaid thermally degraded carbohydrate tobacco substitute to beincorporated in the smoking mixture, admixing said combustible materialwith a predetermined amount of binder and a harmless filler selectedfrom salts wherein the anion comprises formate, oxalate, citrate,tartrate, silicate, carbonate, chloride, sulphate, phosphate, borate,oxide, dioxide or aluminate and the cation comprises sodium, potassium,calcium, magnesium, iron or titanium, the filler being harmless onpyrolysis and present in a proportion of 40 to 65 percent by weight ofthe mixture, and the combination anions and cations in the filler beingsufficient to impart a burning rate correlated to a puff number of 8-12of a machine-made standard Class B British cigarette containing 1.1 g.tobacco, where each puff is of 25 ml. volume in two seconds, followed bya 58 second rest or smouldering period and where the 70 mm. cigarette issmoked to a butt length of 20 mm., and finally fabricating a shapedarticle of the mixture utilising a binder.
 8. A method as claimed inclaim 7 wherein the shaped article is a film, extruded filament or tape.9. A method as claimed in claim 7 wherein the filler comprises calciumcarbonate, calcium borate, sodium borate, calcium orthophosphate,calcium oxalate, iron sulphate, titanium dioxide, magnesium aluminate,sodium aluminium silicate or mixture thereof.